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  • 1
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 21 (1983), S. 1951-1972 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Butadiene is polymerized by cobalt compound-organoaluminum-CS2 catalysts to give highly crystalline syndiotactic 1,2-polybutadiene (s-PB) having melting point up to 216°C. An aluminum-free catalyst, Co(C4H6)(C8H13)-CS2, is also effective. Syndiotactic polymerization with Co(C4H6)(C8H13)-CS2 is not interrupted by the addition of protic substances such as water and alcohol, but is influenced by donor or acceptor substances. The donor molecule, e.g., dimethylsulfoxide or dimethylformamide, decreases the stereoregularity, i.e., syndiotacticity and 1,2 content. An acceptor molecule of organoaluminum with appropriate acidity such as AlEt3-AlEt2Cl or tetraethylaluminoxane increases the molecular weight, stereoregularity, and yield of the polymer. In the presence of CS2 a mixture of cis-PB and s-PB was obtained by using Co(octoate)2-AlEt2Cl-H2O, with molar ratio H2O/Co less than unity. In the case of H2O/Co 〉 1, only cis-PB was obtained. By the addition of donor substances such as ester, ether, nitrile, and AlEt3, s-PB was obtained even when H2O/Co 〉 1. The amount and ratio of cis-PB and s-PB are dependent upon the nature and amount of the additives.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 21 (1983), S. 1989-1995 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A mechanism is proposed for the polymerization of syndiotactic 1,2-polybutadiene (s-PB) with soluble cobalt-organoaluminum-CS2. The proposed active species have structures which consist of side-on coordination of CS2 to cobalt, anti-π-allyl growing end, cisoid bidentate coordination of butadiene, and activation by complex formation with organoaluminum at the nonbonded sulfur of the coordinated CS2. This proposal is based on findings for the aluminum-free catalyst Co(C4H6)(C8H13)-CS2. It is tentatively interpreted that syndiotactic 1,2 polymerization proceeds under the influence of the side-on coordinated CS2, by which the reactivity between the terminal carbons of butadiene and the C3 of the π-allyl end is enhanced.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
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